WO2007136757A2 - Formation mécanique d'un alliage à partir d'un catalyseur d'hydrogénation utilisé pour la réhabilitation de composés contaminés - Google Patents

Formation mécanique d'un alliage à partir d'un catalyseur d'hydrogénation utilisé pour la réhabilitation de composés contaminés Download PDF

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WO2007136757A2
WO2007136757A2 PCT/US2007/011916 US2007011916W WO2007136757A2 WO 2007136757 A2 WO2007136757 A2 WO 2007136757A2 US 2007011916 W US2007011916 W US 2007011916W WO 2007136757 A2 WO2007136757 A2 WO 2007136757A2
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hydrogenation catalyst
milling
catalytic metal
base material
zero
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PCT/US2007/011916
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WO2007136757A3 (fr
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Jaqueline W. Quinn
Christian A. Clausen
Cherie L. Geiger
Brian S. Aitken
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Usa As Represented By The Administrator Of The National Aeronautics And Space Administration
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
    • B22F2009/047—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling by rolling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S420/00—Alloys or metallic compositions
    • Y10S420/903—Semiconductive

Definitions

  • the present invention relates to a method for making a hydrogenation catalyst having a base material coated with a catalytic metal using mechanical milling techniques. This method produces a hydrogenation catalyst that may be used for the remediation of a plurality of contaminated materials, including, but not limited to, polychlorinated biphenyls.
  • PCBs polychlorinated biphenyls
  • PCBs are known to have the chemical structure Ci ⁇ Hio-nCin and, in addition to other chlorinated synthetic aromatic compounds, are of great concern due to their toxicity and persistence in the environment.
  • properties of these synthetic colorless liquids are high chemical stability, low flammability, low thermal and electrical conductivity, and low solubility in water. Atty Dkt. No. KSC- 12978 -2- PATENT APPLICATION
  • PCDDs polychlorinated dibenzodioxins
  • PCDFs polychlorinated dibenzofurans
  • PCDDs have been shown to exist at abnormally high levels in proximity to incinerators burning chlorine-contaminated materials. Cancer rates have also been "well correlated" to both dioxins and proximity to chlorine-contaminated waste burning incinerators.
  • the temperature required to incinerate PCB-contaminated material may be up to 1200 0 C. Additionally, it is expensive to incinerate the PCB-contaminated material and to transport contaminated material.
  • Solvent extraction has also been used to treat PCB-contaminated materials.
  • Organic solvents are used to extract contaminated matrix.
  • extraction is only applied ex-situ and the PCBs are not actually destroyed but transported to another media that has to be further treated.
  • Base-catalyzed decontamination has been used to treat PCB-contaminated material by adding NaHCC» 3 or NaOH to the media.
  • this remediation process is only applied ex-situ due to operating temperatures.
  • Comminution theory is principally concerned with reducing the average size of particles in a sample of crystalline or metallic solid; however, it can also be used to understand mechanical alloying of particles. To accomplish either of these tasks, the most commonly used processes involve ball milling, vibrational milling, attrition, and roller milling.
  • Ball milling is a process in which a material is loaded into a canister partially filled with milling balls. The canister is then rotated at high speed on its major axis so that the balls are held by centripetal force to the inside wall until they reach the highest point inside the canister. Gravitational force then exceeds the upward force of the balls and they fall to the bottom of the canister where they impact other balls and the canister wall.
  • Vibrational milling is a process similar to ball milling except that the milling vessel is vigorously shaken in a back and forth motion or in a back in forth motion in conjunction with a lateral motion that produces a "figure 8" path.
  • This type of milling relies solely on the extremely high-energy collisions between rapidly moving milling balls rather than the collisions between the balls and the canister wall, as described for ball milling. Since vibrator mills can often shake canisters at a rate of approximately 1200 RPMs, often producing ball speeds of upwards of 5 m/s, vibrational milling commonly yields the desired reduction in particle size at a rate one order of magnitude faster than that of ball milling.
  • Attrition milling relies on rapidly spinning paddles to stir the milling balls present in the milling vessel.
  • the rate of size reduction observed is often similar to the rate of reduction observed for vibrator mills of similar size; however, due to the necessity of a cooling system this type of milling is often limited in its capabilities to systems that can be milled in liquid media.
  • Roller milling is a process that relies on fracturing caused by stress induced in the system from the compression of materials between two rolling bars or cylinders. It is most often used for reduction of very coarse materials into less coarse materials that can later be reduced in size by other means. The previous two systems are not discussed quantitatively.
  • L length of mill, cm.
  • J fractional ball filling of mill, dimensionless d s diameter of ball, cm.
  • D diameter of mill, cm. x, x' — particle sizes, cm.
  • Y modulus of elasticity of materials, g. f /sq. cm. and all other terms are constants relating to the material being milled Atty Dkt. No. KSC- 12978 -7- PATENT APPLICATION
  • the rate of particle reduction in vibrational milling is much greater than in ball milling. Additionally, for all types of milling, rate increases with ball density and is greatest when the mill filling ratio (volume of material to be milled/volume of mill) is approximately 10-20% while the volume occupied by milling balls is approximately 40-60% of the total mill volume.
  • re-welding can occur between two similar particles or two dissimilar particles. If re-welding occurs between two similar particles, the net process results in no change of the material nature. If re-welding occurs between two dissimilar particles an alloy particle is created. This alloy particle can then undergo further fragmentation along alternative planes and subsequently be re-welded multiple times. The longer this process is allowed to take place the more dissolved one material becomes in the other. In a brittle-malleable system such as palladium and magnesium, the more ductile magnesium is initially flattened while fragmentation of the more brittle palladium occurs.
  • vibrational milling produces an abundance of very high-energy collisions of grinding material. Since high-energy collisions are necessary for alloying to occur vibrational milling produces the desired result with a greatly enhanced rate.
  • the present invention is directed to a method for making a hydrogenation catalyst using mechanical milling techniques.
  • the hydrogenation catalyst includes a base material coated with at least one catalytic metal.
  • the base material is preferably a metallic and/or mineral material. Most preferably, the base material is a zero-yalent metal.
  • Hydrogenation catalysts having metallic base materials have been shown to act as an excellent catalyst for the dechlorination of polychlorinated biphenyls (PCBs) and other halogenated aromatic compounds. Although previous methods for plating the base material have been used, these prior methods have proven to be inefficient and not cost effective. It has been discovered that mechanical milling techniques can be used to produce a hydrogenation catalyst capable of dechlorinating PCBs and other halogenated aromatic compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.
  • the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron (Fe) or zero-valent magnesium (Mg) particle coated with palladium (Pd) that is impregnated onto a high surface area graphite support.
  • the zero-valent metal particles are microscale or nanoscale zero-valent magnesium or zero- valent iron particles.
  • the microscale particles would have a diameter in the range of 1-3 microns.
  • the preferred nanoscale particles would have a diameter in the range of 20-300 nm. It should be understood that other zero-valent metal particles and combinations may be used.
  • the base material may be selected from a wide variety of minerals including, but not limited to, alumina and zeolites.
  • the catalytic metal is preferably selected from the group consisting of noble metals and transition metals.
  • the preferred catalytic metal is palladium.
  • the preferred mass percent palladium by weight ranges from approximately 0.08-8%, but higher and lower ranges could still yield positive results.
  • Additional catalysts include, but are not limited to, nickel and zinc impregnated into a high surface area conductive support. Atty Dkt. No. KSC- 12978 -9- PATENT APPLICATION
  • the mechanical milling process includes milling the base material with a catalytic metal impregnated into a high surface area support to form the hydrogenation catalyst.
  • a zero-valent metal particle is provided as the base material preferably having a particle size of less than about 10 microns, preferably 0.1-10 microns or smaller, prior to milling.
  • the catalytic metal is supported on a conductive carbon support structure prior to milling.
  • palladium may be impregnated on a graphite support.
  • Other support structures such as semiconductive metal oxides may also be used.
  • the zero-valent metal particle (e.g. microscale magnesium) is preferably ball milled with 1-10% palladium supported on carbon. The preferred mass percent palladium by weight coating the zero-valent metal particle ranges from approximately 0.01-15%, and more preferably 0.08-8%.
  • FIG. 1 is an electron micrograph of a bimetallic particle milled for 1.5 hours beyond the optimum milling time
  • FIG. 2 is an electron micrograph of a bimetallic particle in accordance with the present invention milled for an optimum time period;
  • FIG. 3 is a graph showing the activity of the bimetallic particle over different %Pd in the bimetallic for the optimization of Pd mass loading.
  • FIG. 4 is a graph showing the rate constant of the bimetallic particle over different milling times for the optimization of milling parameters. Atty Dkt. No. KSC- 12978 - 10- PATENT APPLICATION
  • the present invention is directed to a mechanical milling method for making a hydrogenation catalyst having a base material coated with at least one catalytic metal that is impregnated onto a high surface area support.
  • a variety of mechanical milling techniques may be used including, but not limited to, ball milling, vibrational milling, attrition milling, and roller milling.
  • the hydrogenation catalyst may be used for the dechlorination of chlorinated hydrocarbons, such as polychlorinated biphenyls (PCBs), or for the hydrogenation of other industrial chemicals.
  • PCBs polychlorinated biphenyls
  • the hydrogenation catalyst is preferably a bimetallic particle formed by mechanically milling a zero-valent metal with a supported catalytic metal to produce a zero-valent metal particle coated with the catalytic metal.
  • Zero-valent metals are known in the industry as metals in their elemental state.
  • metallic base materials such as zero-valent metal particles are preferred, minerals may also be used as the base material.
  • Preferred mineral base materials include, but are not limited to, transition metal oxides.
  • iron or magnesium is preferred.
  • the catalytic metal is preferably palladium. However, it should be understood that other zero-valent metals and catalytic metals, such as nickel and zinc impregnated on a conductive support, may be used.
  • the preferred metallic base material may include other metallic materials other than zero-valent metal particles. Additionally, one of ordinary skill in the art would appreciate that in addition to the formation of bimetallic particles, other multi-metallic particles may also be fabricated using the present mechanical milling technique.
  • the hydrogenation catalyst is preferably a catalyzed zero-valent metal particle optimized for use in the treatment system and preferably comprises about 0.1% palladium (Pd) impregnated onto a graphite support on zero-valent magnesium (Mg), referred to herein as a Pd/Mg bimetallic.
  • Pd palladium
  • Mg zero-valent magnesium
  • other magnesium-containing bimetallic particles have also been shown to be effective, for example nickel (Ni) supported on graphite and then milled onto magnesium (Mg).
  • the hydrogenation catalyst is a bimetallic particle including a zero-valent magnesium metal coated with graphite supported palladium, herein referred to as a Pd/Mg bimetallic, as it has several advantages over other bimetallic particles.
  • a second preferred bimetallic particle is a zero-valent iron metal coated with graphite supported palladium.
  • One advantage that the Pd/Mg bimetallic has Atty Dkt. No. KSC- 12978 - 1 1 - PATENT APPLICATION
  • the preferred graphite supported palladium catalyst acts as a hydrodehalogenation catalyst by dissociating hydrogen gas (formed from the reaction of Mg 0 or Fe 0 with water or another proton donor), that is adsorbed onto the palladium surface, to produce atomic hydrogen.
  • hydrogen gas formed from the reaction of Mg 0 or Fe 0 with water or another proton donor
  • bimetallic particles were previously prepared by the deposition of palladium onto the magnesium surface by reaction of zero- valent magnesium with palladium acetate. However, to produce reasonable kinetics in this previous technique, a 4% palladium coating was required. Since this was not cost effective, mechanical alloying was attempted.
  • Examples provide a preferred embodiment of mechanical milling that may be varied by one of ordinary skill in the art. Not only may other mechanical milling techniques be used, but other operating conditions may be used to provide a hydrogenation catalyst in accordance with the present invention.
  • the first attempts at producing active mechanically alloyed Pd/Mg bimetallic were carried out using a Spex Centiprep 8000 high-energy vibrator mill. Ball-to-mass ratios and loading levels were not considered while semi-optimizing the process. Milling time and percent palladium were the only variables considered. Using 6g total mass milling material with three 1Og stainless steel milling balls in a 54.5mL Tungsten Carbide milling vessel filled under N 2 was found to be the optimum condition for producing the Pd/Mg bimetallic.
  • the dechlorination ability of the bimetallic particles was analyzed for optimization.
  • Crimp top vials were set up with Ig neat bimetallic particles and 1OmL 6ppm Arochlor 1260 water 'solution. The system was allowed to react for a given time and extracted in hexane. The extraction method was conducted by placing the samples in an ultrasound bath for 30 minutes prior to the extraction. 5mL of hexane was added to the vial. The vial was then placed in the ultrasound bath for an additional 30 minutes. The vials were removed from the bath and centrifuged for 1 minute. The hexane layer (5mL) was drawn off. All the samples were then dried with Na 2 SO 4 .
  • bimetallic particle produced using the mechanical milling technique appeared to work as well or better than bimetallic particles prepared from pallamerse. This was much more economical, however mass production of the bimetallic particle was impossible using a mill that produced only six grams of material at one time.
  • An efficient large-scale mechanical process for preparation of the bimetallic particles was necessary to upgrade to a field-scale project and will be discussed in greater detail below.
  • EXAMPLE Large Scale
  • Tungsten carbide is used as the milling vessel material in most high-energy, small-scale mills because it is extremely durable and does not break down over time or cause the introduction of contaminates into the milling material.
  • the use of an extremely durable milling vessel was not necessary in this case because the introduction of some contaminates would not appreciably affect the reactivity of the metal, thus galvanized steel pipes (purchased from Ace Hardware with internal diameter-5.03 cm, length- 17.8 cm) with steel end caps were used.
  • Steel ball bearings (mass-22.3 grams each, volume- 1.6 cm 3 each) were chosen as the grinding matrix. Since the paint shaker chosen operates at approximately 600 RPMs (as opposed to 1250 RPMs observed for the Spex Centi-prep) longer milling times were necessary.
  • PCB degradation The PCBs were extracted from solution by adding 5mL Fischer
  • FIG. 1 shows a bimetallic particle milled for 1.5 hours beyond optimum time.
  • FIG. 2 shows a bimetallic particle milled for optimum time period.
  • PCB concentration Since this apparatus is more sensitive, it allowed for a more accurate measurement.
  • the experimental setup was similar to the setup used in the small-scale analysis. Single congeners were used for some studies due to the ease of analysis versus
  • Pd bimetal 0.083, 0.11, and 0.016% Pd bimetal was prepared and tested for degradation rate as follows:
  • FIG. 4 provides the results that a 30-minute mill time was found to produce the most active bimetal.

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  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un catalyseur d'hydrogénation comprenant un matériau de base enduit d'un métal catalytique, ledit catalyseur étant fabriqué en utilisant des techniques de broyage mécanique. Les catalyseurs d'hydrogénation constituent d'excellents catalyseurs pour la déshalogénation de composés contaminés et la réhabilitation d'autres composés industriels. Le catalyseur d'hydrogénation est de préférence une particule bimétallique comprenant des particules métalliques de valence nulle enduites d'un matériau catalytique. La technique de broyage mécanique est plus simple et moins coûteuse que les procédés utilisés auparavant pour la fabrication de catalyseurs d'hydrogénation.
PCT/US2007/011916 2006-05-19 2007-05-18 Formation mécanique d'un alliage à partir d'un catalyseur d'hydrogénation utilisé pour la réhabilitation de composés contaminés WO2007136757A2 (fr)

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US74768106P 2006-05-19 2006-05-19
US60/747,681 2006-05-19
US11/749,767 US7842639B2 (en) 2006-05-19 2007-05-17 Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds
US11/749,767 2007-05-17

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US8288307B2 (en) 2012-10-16
WO2007136757A3 (fr) 2008-01-10
US20110172082A1 (en) 2011-07-14
US7842639B2 (en) 2010-11-30

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